Microwave spectrum and barrier to internal rotation of 1-chloro-2-butyne

Abstract

Rotational transitions of the μa and μb type have been identified with microwave-microwave double resonance measurements for 1-chloro-2-butyne in the ground vibrational state. In the first excited state of the methyl torsion only μa-type transitions have been identified. The A-type transitions of the ground vibrational state can be described perfectly by the rigid rotor approximation with centrifugal corrections. Using the internal axis method the barrier to internal rotation was determined from the A,E splittings: V3 = 10.05 ± 0.09 cm−1. A model which allowed for geometry relaxation upon internal rotation was used to fit one set of parameters to the transition frequencies of both ground state and first excited torsional state. The sixfold contribution to the barrier was found to be negligible: V6 = −0.4 ± 0.3 cm−1.